CN102024568B - Manufacture method of high-capacity inorganic super capacitor electrode plates - Google Patents
Manufacture method of high-capacity inorganic super capacitor electrode plates Download PDFInfo
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- CN102024568B CN102024568B CN2010102165689A CN201010216568A CN102024568B CN 102024568 B CN102024568 B CN 102024568B CN 2010102165689 A CN2010102165689 A CN 2010102165689A CN 201010216568 A CN201010216568 A CN 201010216568A CN 102024568 B CN102024568 B CN 102024568B
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- ultracapacitor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a manufacture method of high-capacity inorganic super capacitor electrode plates. The improvement lies in that a fiber compound accounting for 0.1 to 5wt% of the total weight is added to positive and negative electrode active substances, the thickness of a coated electrode plate reaches 3-10mm, and membranes are glued and sealed on the circumference of the electrode plate with an adhesive after the positive and negative electrode plate is wrapped by the membranes. The fiber compound comprises the following ingredients in content: 40-65% of graphite fiber and/or carbon fiber, 30-40% of nylon fiber and/or polyester fiber and 1-20% of polyvinyl alcohol. Acrylic acid modified epoxy glue or epoxy resin glue serves as the adhesive. The manufactured electrode plates are used for manufacturing inorganic super capacitors and can ensure that energy stored by the inorganic super capacitors can be largely improved and the inorganic super capacitors have the capacity more than 130,000 F, and the mass ratio power more than 12wh/kg, and can meet the use requirements of electric automobiles and new energy fields of solar energy, wind energy and the like. When the super capacitor is used, the system is simplified, and the running cost is low.
Description
Technical field
The present invention relates to a kind of manufacture method of big capacity inorganic type ultracapacitor pole piece, belong to ultracapacitor category in the energy storage technology.
Background technology
Ultracapacitor is a kind of novel green, environmental protection accumulation power supply product between physics electric capacity and chemical power source.Ultracapacitor stores energy in electrode material and electrolyte interface, comprises faraday's electric capacity of the accurate two dimension in electric double layer capacitance and interface, thereby has the capacitance of superelevation, discharges and recharges power and electric current, extraordinary cryogenic property greatly; Because electrochemical reaction does not take place in the cyclic process the special energy storage mechanism of ultracapacitor, the electrode performance decay is minimum.Secondary cell application in the market is commonplace, and like lead-acid battery, Ni-MH battery, nickel-cadmium cell, lithium battery etc., ultracapacitor is compared with secondary cell has special advantages.The secondary cell energy storage is bigger, and specific energy is high, has stable application market field.But secondary cell also exists, and more weak point such as cycle life are relatively shorter, high temperature performance is poor, the nickel-cadmium cell lead-acid battery contains heavy metal and environment produced shortcomings such as pollution; The appearance of ultracapacitor has remedied secondary cell deficiency in these areas; Thereby also more and more receiving people's attention, lot of domestic and foreign enterprises and scientific research institution carry out ultracapacitor Products Development and research.
An important application direction of ultracapacitor is fields such as electric automobile, track traffic, wind power generation energy storage, solar power generation energy storage, requires the energy storage product that bigger energy storage and long useful life will be arranged in these fields.The conventional accumulators energy storage is bigger, but because there is decay in its both positive and negative polarity generation chemical reaction, useful life is shorter, has bigger drawback; Ultracapacitor cycle life reaches 100,000 times, compare very advantageous with storage battery, but energy storage is relatively low, thereby the market active demand has more high power capacity and the ultracapacitor product of energy storage greatly.
Ultracapacitor in the market is mainly the organic system ultracapacitor; This kind ultracapacitor is mainly towards fields such as consumer electronics, toy, automobile audios; Mostly product capacity is that several farads are to the hundreds of farad; Have excellent charging and discharging, the gentle cycle life performance of height, but capacity is very little, can't satisfies the demand aspect big capacity energy storage.
Patent CN02257929.X has introduced a kind of high capacity rectangular ultracapacitor, and its housing is the rectangle cube, and positive/negative plate is made up of the conduction coat on foaming Ni substrate and surface thereof, links to each other with the screw leading-out terminal again, and case top is provided with safety valve.This ultracapacitor has in light weight; Power and capacity are bigger, and cryogenic property is good, and advantage such as have extended cycle life; Its manufacturing articles capacity can reach 5000F, can satisfy electric motor car quicken, start, high power during climbing requires and the requirement on electric performance of other high-power device.But, because it requires storage power very big, as adopt common ultracapacitor then to need a large amount of ultracapacitor connection in series-parallel to use, to reach the energy storage requirement at new energy fields such as emerging electric automobile, solar energy, wind energies.Complexity and cost that this has just increased system, make ultracapacitor in big capacity energy storage field application difficult.
The capacity of ultracapacitor is big inadequately at present, and key is the manufacture method defectiveness of condenser plate, shows that mainly pole piece thickness is less; Pole piece coat material property is poor; Exposed around the pole piece, cause the pole piece internal resistance higher, conductivity is bad; Easyly ftracture, dry linting, delamination, these problems are anxious to be solved.
Summary of the invention
The technical problem that the present invention will solve is that to overcome existing capacity of super capacitor big inadequately; Operation defect of high cost when a large amount of capacitor connection in series-parallel are used; Provide that a kind of storage power is big, operating cost is low, can satisfy the manufacture method of the big capacity inorganic type ultracapacitor pole piece of electric automobile and new energy field demands such as solar energy, wind energy.
Technical scheme of the present invention is: the manufacture method of big capacity inorganic type ultracapacitor pole piece; Be included on the positive/negative plate coating both positive and negative polarity active material and positive/negative plate is coated with barrier film; Its improvements are: be coated with in the used both positive and negative polarity active material that to add the mass percent that accounts for its total amount be 0.1%～5% fibre composites, make pole piece thickness reach 3～10mm during coating; Positive/negative plate sticks with glue agent with the barrier film adhering and sealing to around the pole piece after coating with barrier film again.Said fibre composites is to be in 1%～3% the poly-vinyl alcohol solution with joining mass percent concentration behind one or both and nylon fiber in graphite fibre, the carbon fiber, one or both premixs in the polyester fiber; Stirred 12～24 hours fast down at 50～80 ℃, dehydration by evaporation makes after grinding then.
Further scheme is: in the said fibre composites, the mass percentage content of each component is: graphite fibre and/or carbon fiber 40～65%, nylon fiber and/or polyester fiber 30～40%, polyvinyl alcohol 1～20%; Said adhesive adopts acrylic acid modified epoxy glue or epoxide-resin glue.
The pole piece thickness of common ultracapacitor is many below 1mm, and pole piece thickness increase then internal resistance becomes big rapidly, and blocked up pole piece is prone to cause phenomenons such as cracking, dry linting, delamination simultaneously, influences the product serviceability.The present invention has prepared fibre composites, and joins in the both positive and negative polarity active material, efficiently solves these problems, makes monolithic pole piece thickness increase, and the active matter quality that is coated with on the pole piece improves greatly.This fibre composites has good conductivity, can improve pole piece self-conductive property, reduces internal resistance.The adding of fibre composites has simultaneously improved pole piece intensity and toughness, in the production and the course of processing, is difficult for dry linting, cracking, active material is connected closely with collector, thereby makes jumbo ultracapacitor product.
At present ultracapacitor barrier film method for coating adopts the folding or stacked coating of S type more, and top and bottom and the barrier film of pole piece compress, but then can not the coating all around of pole piece.Ultracapacitor use for a long time and overcharge use the back pole piece around owing to there is not diaphragm blocks, the dry linting phenomenon very easily comes off.Phenomenons such as the powder that comes off is mixed in the electrolyte, has brought impurity into and has caused self discharge bigger than normal, and leakage current is serious.The present invention adopts acrylic acid modified preferably epoxy glue of alkali resistance or epoxide-resin glue that the barrier film around the pole piece is bonded to together, with sealing around the pole piece, has effectively prevented the generation of above-mentioned phenomenon, has improved big capacity ultracapacitor properties of product.
The pole piece of being processed by the present invention makes the ultracapacitor storage power and significantly improves, and can satisfy the instructions for use of electric automobile and new energy fields such as solar energy, wind energy, and can make system simplification, and operating cost is low.
Embodiment
Through embodiment, the present invention is described further below.
Embodiment 1
Get the 100g graphite fibre and the 50g nylon fiber is pre-mixed stirring at beaker, the poly-vinyl alcohol solution 1000g of configuration 1% stirs and adds graphite fibre and nylon fiber down, slowly is warming up to 80 ℃, and (200r/min) stirred 12 hours fast.Moisture is sloughed in evaporation then, makes the fibre composites of puffy after the grinding.
Press common process and make the ultracapacitor anode and cathode slurry, the mass ratio that fibre composites accounts for the both positive and negative polarity active material is 0.5%, when the preparation slurry and PTFE binding agents such as (polytetrafluoroethylene) together add, and the proper extension mixing time is more than 6 hours.Above-mentioned anode and cathode slurry of becoming reconciled is coated on the nickel foam, and nickel foam thickness is 1.5mm, and hole count PPI value is 110, coats pole piece and is of a size of 140mm * 140mm, and thickness is 3mm.
Positive/negative plate is all adopted the folding coating of polypropylene diaphragm, and around pole piece, be stained with a small amount of epoxide-resin glue, the levels barrier film is bonded to together, at room temperature solidified 12 hours.
With the positive/negative plate stack combinations, putting into overall dimension (length * wide * height) is 160mm * 80mm * 170mm capacitor casing at last, injects the KOH solution of 6.5mol/L, and encapsulating housing makes big capacity inorganic type ultracapacitor.
The ultracapacitor of processing is detected with U.S.'s BITRODE charging-discharge tester system, and this product capacity reaches 14.2 ten thousand F, and quality is than power 12.6Wh/Kg, and leakage current value is 96mA.
Embodiment 2
Get 80g carbon fiber and 30g nylon fiber, the 30g polyester fiber is pre-mixed stirring at beaker, configuration 2% poly-vinyl alcohol solution 1000g stirs and adds graphite fibre and nylon fiber down, slowly is warming up to 60 ℃, stirs fast 20 hours.Moisture is sloughed in evaporation then, makes the fibre composites of puffy after the grinding.
Press common process and make the ultracapacitor anode and cathode slurry, the mass ratio that fibre composites accounts for the both positive and negative polarity active material is 2%, when the preparation slurry and binding agent such as PTFE together add, and the proper extension mixing time is more than 6 hours.Above-mentioned positive and negative slurry of becoming reconciled is coated on the nickel plated steel strip, and the steel band thickness of coating is 0.01mm, coats pole piece and is of a size of 140mm * 140mm, and thickness is 8mm.
Positive/negative plate is all adopted the folding coating of polypropylene diaphragm, and around pole piece, be stained with a small amount of epoxide-resin glue, the levels barrier film is bonded to together, at room temperature solidified 12 hours.
With the positive/negative plate stack combinations, putting into overall dimension (length * wide * height) is 160mm * 80mm * 170mm capacitor casing at last, injects the KOH solution of 6mol/L, and encapsulating housing makes big capacity inorganic type ultracapacitor.
The ultracapacitor of processing is detected with U.S.'s BITRODE charging-discharge tester system, and this product capacity reaches 15.3 ten thousand F, and quality is than power 13.2Wh/Kg, and leakage current value is 115mA.
Embodiment 3
Get 40g graphite fibre, 50g carbon fiber and 70g nylon fiber and be pre-mixed stirring at beaker, the poly-vinyl alcohol solution 1000g of configuration 3% stirs adding graphite fibre and nylon fiber down, slowly is warming up to 50 ℃, stirs fast 24 hours.Moisture is sloughed in evaporation then, makes the fibre composites of puffy after the grinding.
Press common process and make the ultracapacitor anode and cathode slurry, the mass ratio that fibre composites accounts for the both positive and negative polarity prescription is 0.1%, when the preparation slurry and binding agent such as PTFE together add, and the proper extension mixing time is more than 6 hours.Above-mentioned anode and cathode slurry of becoming reconciled is coated on the nickel foam, and nickel foam thickness is 1.5mm, and hole count PPI is 110, coats pole piece and is of a size of 140mm * 140mm, and thickness is 5mm.
Positive/negative plate is all adopted the folding coating of polypropylene diaphragm, and around pole piece, be stained with a small amount of acrylic acid modified epoxy glue, the levels barrier film is bonded to together, at room temperature solidified 12 hours.
With the positive/negative plate stack combinations, putting into overall dimension (length * wide * height) is 160mm * 80mm * 170mm capacitor casing at last, injects the KOH solution of 6.5mol/L, and encapsulating housing makes big capacity inorganic type ultracapacitor.
The ultracapacitor of processing is detected with U.S.'s BITRODE charging-discharge tester system, and this product capacity reaches 13.5 ten thousand F, and quality is than power 12.2Wh/Kg, and leakage current value is 86mA.
Claims (3)
1. the manufacture method of one kind big capacity inorganic type ultracapacitor pole piece; Be included on the positive/negative plate coating both positive and negative polarity active material and positive/negative plate is coated with barrier film; It is characterized in that: be coated with in the used both positive and negative polarity active material that to add the mass percent that accounts for its total amount be 0.1%～5% fibre composites, make pole piece thickness reach 3～10mm during coating; Positive/negative plate sticks with glue agent with the barrier film adhering and sealing to around the pole piece after coating with barrier film again; Said fibre composites is to be in 1%～3% the poly-vinyl alcohol solution with joining mass percent concentration behind one or both and nylon fiber in graphite fibre, the carbon fiber, one or both premixs in the polyester fiber; Stirred 12～24 hours fast down at 50～80 ℃, dehydration by evaporation makes after grinding then.
2. press the manufacture method of the said big capacity inorganic type ultracapacitor pole piece of claim 1; It is characterized in that in the said fibre composites; The mass percentage content of each component is: graphite fibre and/or carbon fiber 40～65%; Nylon fiber and/or polyester fiber 30～40%, polyvinyl alcohol 1～20%.
3. by the manufacture method of the said big capacity inorganic type ultracapacitor pole piece of claim 1, it is characterized in that said adhesive adopts acrylic acid modified epoxy glue or epoxide-resin glue.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010102165689A CN102024568B (en) | 2010-06-30 | 2010-06-30 | Manufacture method of high-capacity inorganic super capacitor electrode plates |
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| CN2010102165689A CN102024568B (en) | 2010-06-30 | 2010-06-30 | Manufacture method of high-capacity inorganic super capacitor electrode plates |
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| CN102024568A CN102024568A (en) | 2011-04-20 |
| CN102024568B true CN102024568B (en) | 2012-06-06 |
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| CN104167535A (en) * | 2013-05-17 | 2014-11-26 | 无锡华臻新能源科技有限公司 | Lithium ion battery slurry capable of resisting cracking and powder-falling after coating and preparation method thereof |
| CN104549930A (en) * | 2013-10-28 | 2015-04-29 | 无锡华臻新能源科技有限公司 | Lithium ion battery electrode with reinforcing fiber on surface and coating method |
| CN112981717B (en) * | 2021-02-05 | 2022-04-05 | 广州金立电子有限公司 | Capacitor diaphragm and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101656155A (en) * | 2009-09-22 | 2010-02-24 | 南京双登科技发展研究院有限公司 | Method for making high-capacity organic ultracapacitor in flexible package |
| CN101667637A (en) * | 2009-09-22 | 2010-03-10 | 南京双登科技发展研究院有限公司 | Method for manufacturing lead-carbon ultracapacitor battery cathode |
| CN101707143A (en) * | 2009-11-10 | 2010-05-12 | 苏州大学 | hybrid electrochemical capacitor |
| CN101719420A (en) * | 2009-11-06 | 2010-06-02 | 苏州大学 | Super capacitance storage battery |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101656155A (en) * | 2009-09-22 | 2010-02-24 | 南京双登科技发展研究院有限公司 | Method for making high-capacity organic ultracapacitor in flexible package |
| CN101667637A (en) * | 2009-09-22 | 2010-03-10 | 南京双登科技发展研究院有限公司 | Method for manufacturing lead-carbon ultracapacitor battery cathode |
| CN101719420A (en) * | 2009-11-06 | 2010-06-02 | 苏州大学 | Super capacitance storage battery |
| CN101707143A (en) * | 2009-11-10 | 2010-05-12 | 苏州大学 | hybrid electrochemical capacitor |
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